Method of treating fibrous



Rei asued Sept. 25; 1934 UNITED STATES PATENT; or Ics 19,325 DIETHOD F TREATING FIBROUS MATERIAL Leo A. Goodman, Brooklyn, N. Y. v v

No Drawing. Original No. 1,829,702, dated om; ber 27, 1931, Serial No. 442,443, April 7, 1930.

Application for reissue October 37 Claims.

The present invention relates generally to the treatment of vegetable fibrous material with a soluble cellulose derivative, and has particular l0 fibres having certain desirable characteristics and properties present in Japanese tissue paper" of' by any reagents except those which have a solvent actionupon the fibrous base or'the cellulose. Another function of the present method and the one which at the present time is considered more important and useful is that of the production of a material which will afford an excellent and highly eflicient substitute for the natural gut of animals, such asused for sausage casings.

This material simulates the properties of the natural gut, in appearance, tensile strength-elasticity, flexibility, pliability and porosity, It has also, like the natural gut, the unique properties of expansion when moistened and-contraction when dried. This material is especially adaptv able when formed into a containerior the purposeof preparing bolognas, sausage or any other kind of food product for which the natural gut may be used, and has ,been found by the most exacting tests to be especially practical where I smoking and boiling processes are followed. Furthermore, the material excels -the natural gut because it is more sanitary and clean.

' Many attempts have heretofore been made to produce an artificial casing simulating in appearance and qualities that of the natural gut, but these attempts have all proven unsuccessful for one reason or another. It is known that in the prior art the use has been made of what is known as cellulose ,hydrate for producing a casing which has its cellular structure entirely destroyed to render it non-fibrous. However, exhaustive experiments have shown that a practical and workent in the natural gut casing. Because of these 1, 1933, Serial able casing cannot be made under this process mainly'for the reason that, without a fibrous base, the material, when formed into a tubular container, would not withstand the rigorous tests to which it must be subjected when filled with meats by means of compressed air, steam, or hydraulic pressure.- The 'impracticability of this casing lies largely in the fact that it loses most of its tensile strength when damp or wet. Because of this characteristic, even if, by taking 35 great precautions to keep the casing dry, the tendency to burst could belessened during the filling process, still the wet meat, which would necessarily wet the casing would have a tendency 3 to weaken it sufiicientlyto cause it to fall'from the racks during the sm'okingprocess. Also, in

the case of the non-fibrous material, any 'imperfections, such as small holes or tears in the casing, will render the casing uselessfor filling ,This is because any force exerted at the point of imperfection will cause. a progressive enlargement of the hole or a progressive lengthening of the tear. On theother'hand, the casingmade under the new process, because of its fibrous base, i has increased tensile strength even when wet. Further, it is because'ofuthis-fibrous base that the further progress ofany'break or tear is retarded and'its area restricted. The new casing will expand when wet and contract when dry and thus simulates certain desirable characteristics inhervarious essential characteristics the meat in the, container adheres to the inner surface from the beginning of the treatment until the end forthe reasonthat if the meat content should dry and shrink or dampen and expand the cashig will do likewise in a uniform and satisfactory manner.

It has been customary, in the manufacture of I bolognas and the like, to imprint a suitable stamp upon the exterior surface of the natural gut container, after filling, or to attach a printedidentification tag at one end of the filled container. This practice has led to much deceit and fraud as it is a relatively easy matter for unscrupulous rial itself.

, vents.

dealers to alter or change an identification mark. This objection may be overcome by the present method, for the material produced thereby is a synthetic product and it has been discovered that an imprintation with ink or the like may be made upon the fibrous base and beneath the outer layers or surfaces of thefinished product, which imprlntation will be as permanent as the mate- One of the essential features of the present invention is the treatment of a, vegetable fibrous base with a soluble cellulose, such as a suitable ester or ether, a solution of either of which may be prepared by dissolving in non-alkaline or inert organic solvents, or other suitable solvents. After the base has beentreated with the cellulose derivative, it is subsequently subjected to a suitable chemical treatment resulting in the partial Y desired to set forth at some length what is underst to be the meaning of the terms cellulose,

solu 1e cellulose, and insoluble cellulose. According to the most recent scientific under-. standing, the general term cellulose means a colloidal material forming the framework of all.

vegetable cells. It has the same empirical formula (CaHmOsh: as starch and like the latter belongs to the general class of organic bodies known as carbohydrates. Like starch, it may be hydrolyzed, though more slowly, to glucose, but, unlike starch, cellulose occurs as fibres instead of granules, is substantially unafiected 'by boiling water and is not stained by iodine. P. Klason (Svensk Papers, Tid. 27, 261-4, 1924) suggests that cellulose be defined as a carbohydrate which at 98 C. is not soluble in a digesting acid containing 13 I grams of whollyfree $0: per liter.

The formation of a soluble cellulose body may be brought about by the resolution of any cellulose material by one of two general methods, to wit: (1) by the dispersion of the cellulose through liquidsolutions of special chemical reagents, and (2) by the bringing into solution cellulose esters or ethers by means of suitable sol- By pursuing the first general method, the following chemical reagents have been found to bring about the desired resultsz-Schweitzers reagent, Cu-NI-h method; a 40% solution of 21101: at C.; a K01 solution of Zn in the cold;

-HCl solutions of SbCl: (concentrated), SbCls, .BiCb, and Tick; also acid solutions of CaClz,

Bach, LiCl, CaBrz, LiBr and MgBra; also hot solutions of thiocyanates (sulfocyanides) as Ca thiocyanate; The exact mechanism of bringing the cellulose into solution'is not very well understood. It is claimed, however, that whenever the chemical action is allowed to proceed to a point beyond which there is a degradation of the cellulose molecule, the colloidal power of the solution is diminished and, of course, whenever; there is a degradation of the molecule it will be impossible to regenerate the original cellulose molecule when the reagents causing the dispersion are removed.

lit ,has been found that, by the union of cellulose with acid or'alcohol'radicals formng esters and ethers, if care is taken to avoid degradation of the cellulose molecule, there is no diminishing of the colloidal power of the original cellulose homogeneous fabric.

and that substantially unmodified cellulose may be regenerated. These esters and ethers are 501- uble in a great number of organic liquids as ketones, esters, phenols, cyclic alcohols, and binary and ternary mixtures of non-solvents. The viscosity varies with the kind and nature of ester, the kind, nature and amount of the plasticizer used with the ester, the physical constants of the solvent or solvent combination, the time and temperature, and whether the viscosity has been artifically diminished. An unmodified cellulose gives a more viscous solution.

The term insoluble cellulose, as used in the present invention, is employed to indicate the regenerated or recovered cellulose which-may be obtained in the case of the first-mentioned method, by the precipitation or the removal of the chemicals causing dispersion, or, in the second method, by the hydrolysis of the ester or the decomposition of the ether. It should bementioned,however, that the first method would not in general be applicable to this invention, prlmarily because the same chemicals which cause the dispersion of the cellulosein solution would probably have some dispersive action on the cellulose in the fibre, thereby weakening it. It has beenfound by experiment, that the especially suitable soluble cellulose derivatives are those obtained by the solution of a cellulose ester or ether in organic solvents which are inert or have no chemical action-on the structure of the cellulose molecule. It has also been found that even water has a tendency to soften and disintegrate the matted structure of the fibrous base.

Broadly, the materal produced by the present invention may be prepared by first impregnating a vegetable fibrous structure with a suitable soluplants mitzumata, kodzu,'or gampi, or other sim-.

ilar plants. Papers made of the fibres of these plants have been found especially suitable for carrying out the invention becauseof their ability to absorb and form a unitary appearing body with the solublegcellulose derivatives and after regeneration of the cellulose to forma strong "cated below. None of the chemicals or materials used in the present method are toxic or injurious to health and the final resulting product comprising fibrous material, cellulose, or any other suitable finishing agent is not only non-toxic but edible. v

Several methods may be followed in obtaining a container for receiving meats, but in any case It will be understood, how.-v

it is essential that in theinitial step the cellulose ester be intermingled with the fibrous material,

- for example:

' whole finally cast into a suitable mold and shaped to form a tube or otherwise manipulated. v

. If it is desired to make indestructible imprintations, suitable imprints -'may be made'either on the fibrous material prior to impregnation, or under certain conditions it may be produced after the impregnated cellulose acetate has dried, but prior to subjecting the ester to further treatments. In this connection, it is pointed out that, if the method is to be employed for the preservation of written or printed records, as previously suggested, the imprintations are preferably made on the fiat sheets and the formation of the sheets into tubes is then an unnecessary step in the operation.

Irrespective of the particular method employed, theultimate object is to obtain a substantially cylindrical tube of the fibrous base impregnatedwith the soluble cellulose derivative,

The resulting impregnation should give a translucent, non-porous material practically unaffected by hot or" cold water. Especially satisfactory results are attained by dissolving the ace- I tate in proper solvents'and plasticizers until the desired viscosity and otherdesired physical characteristics are obtained. In order to save thelabor ot'tying off one end of the tube with twine, the resulting impregnated fibrous cylindrical tube may be constricted or closed at one end by first softening it with a suitable solvent and then twisting it until a closed nipple form is produced at this end. The end is then permitted to again dry, thus forming a solid body which .does not .become untwisted.

After completely drying the'impregnated material by allowing the volatile solvents to evaporate, the tube, with or without the form of clo-.

' sure just described, is then subjected to the treatment by a sufiiciently concentrated alkali metal hydroxide as'so'dium hydroxide, dissolved in a1- cohol or other appropriate solvent, until the ester is substantially completely hydrolyzedthe celiulose remaining in'a more or less modified form as an insoluble deposition upon the fibrous structuralbase, rendering the resultant material porous and capable of contracting and expanding without rupture. I

After removing the alkali the container may be treated with various liquids, such as non-toxic alcohol, parafiln' hydrocarbons, edible .oils and fats, or any agent which will aid in imparting a greater transparency or better finish to the product.

What is claimed is:-'v

1. The method of treating a fibrous base pre pared fr'ommitzumata, kodzu, gampi or other.

similar plants, which comprises impregnating the base with a .soluble cellulose derivative, a soluorganic solvents, and then substantially or completely regenerating the cellulose'in a hydrated condition as an insoluble deposition'upon the fibrous base. I

2. The method of treating a fibrous base prepared from mitzumata, kodzu, gampi or other.

similar plants, which comprises impregnating the base with a solution of cellulose acetate, and then subjecting the impregnation to the action of an alkaline solution to substantially or completely regenerate the cellulose as an insoluble depositionupon the fibrous base.

3. The method of treatingfa fibrous base pre- 4. The method of treating a fibrous base pre-' pared from mitzumata, kodzu, gampi or other.

similar plants, which comprises impregnating the .base with a solution of cellulose acetate, drying the impregnation, and then subjecting the impregnation to the action of an' alkaline solution to regenerate the cellulose as an insoluble body upon the fibrous base.

5, The method of treating a fibrous base prepared from mitzumata, kodzu, gampi or other similar plants, which comprises making ',im-.

printatio'ns thereon, impregnating the fibrous base with a solution of cellulose acetate, and then subjecting the impregnation to the action of an alkaline solution to regenerate the cellulose as an insoluble deposition upon the fibrous base.

6. The method of producing a container for -edible products, which comprises forming a sheet of fibrous material prepared from mitzumata, kodzu, gampi or other similar plants into a tube,

impregnating said tube with a cellulose derivative, a solution of which is prepared by dissolving'in solvents for the cellulose derivative, and then regenerating the cellulose as an insoluble deposition upon the fibrous base.

7. The method of producing a container for edible products, which comprisesforming a sheet of fibrous material prepared from mitzumata, kodzu, gampi or other similar plants intoa tube, making imprintations on said tube, impregnating said tube with a cellulose derivative, a solution of whichis prepared by dissolving in inert organic solvents, and then regenerating the cellulose gody as an insoluble deposition upon the fibrous ase.

8. The method of producing a container for edible products, which comprises forming a sheet of vegetable fibrous material into a tube, impregnating said tube with a soluble cellulose derivative, .a solution of which is prepared by dissolving in inert organic solvents, twisting the end of the tube to form a closure therefor, permitting the tube to dry, and then regenerating the cellulose as an insoluble body upon the fibrous base. I

9. The method of producing a container for edible products, which comprises forming a sheet of vegetable fibrous material into a tube, impregnating saidtube with a soluble cellulose ester, twisting the end of the tube to form aclosure therefor, permittingthe tube to dry, and then regenerating the cellulose as an insoluble deposition upon the fibrous base.

ias

edible products, which comprises forming a sheet of vegetable fibrous material into a tube, im-

" Pr snating the tube with a solutionof cellulose acetate, twisting the end of the tube to form a closure therefor, permitting the tube to dry, andthen subjecting the tube to the action, of an alkaline solution to regenerate the cellulose as an insoluble deposition upon the fibrous base.

11. The method of producing a casing for meat products, which comprises forming a sheet of. fibrous material prepared from mitzumata, kodzu, gampi or other similar plants into a tube, applying identifying marks upon said tube, impregnating said tube with a solution of cellulose ester, twisting the end of the tube to close it, drying the tube, and then regenerating the celluloseas an insoluble deposit upon the fibrous material.

12. The method of producing a fabric suitable for use as a covering for edible products, which comprises impregnating a sheet of fibrousmaterial prepared from mitzumata, kodzu, gampi or other similar plants with a solution of' cellulose acetate, drying said sheet, and regenerating the cellulose as an insoluble deposition upon said sheet.

- 13. The method in producing a casing suitable for use as a -covering i'or edible products, which I comprises impregnating a sheet of fibrous material prepared from mitzumata, kodzu, gampi or other similar plants with a solution of cellulose acetate and a suitable plasticiaer to form a flexible transparent material unafiected by water.

14. The method of producing. a fabric suitable for use as a covering for edible products, which comprises impregnating a sheet 01 fibrous material prepared from mitzumata, kodzu, gampi or other similar plants with a solution of cellulose acetate and a suitable plastioizer to form a flexible translucent material. and regenerating the cellulose as an insoluble deposition upon said base.

15. The method of producing a container for Edible products, which comprises impregnating a,

sheet of vegetable fibrous material with a solution of a cellulose deriva ive in inert organic solvents, forming the shee into a tube, said im Dregnating and forming being performed in either order, twisting one endof the tube to close the same, drying the impregnated tube, and then regenerating the cellulose as an insoluble deposit upon the fibrous base. a

18. The method of producing a container for edible products, which comprises impregnating a sheet of vegetable fibrous material with a solution of cellulose acetate, forming the sheet into a tube, said impregnating and forming being performed in either order, twisting one. end of the tube to close the same, drwing'the impregnated tube, and then regenerating the cellulose as an insoluble deposit upon the fibrous base.

17. As an article of manufacture, a casing for food products comprising a fibrous base prepared from rnitzumata; kodzu, gampi' or other similar plants and having thereon a deposit of regenerated cellulose prepared from de-esterified acetated cellulose.

18. As an article ofmanufacture, a c for food products comprising a fibrous base prepared from mitzumata, kodzu, gampi or other similar plants and having thereon a deposit of regenerated cellulose obtained from de-esterified acety- 'lated cellulose, upon which and in which is a permanent imprintation.

19. As an article of manufacture, a casing for food.- products comprising a branded fibrous base 20. A method of producing a container for edible purposes containing no nitrogenous components comprising forming a-sheet of vegetable fibrous material into substantially tubular form, impregnating said tube with cellulose acetate in solution in a non-aqueous solvent, de-esterifying the cellulose acetate by ways now known'until substantially allot the acetic acid radical has been removed therefromfinally treating the material in a parailin hydrocarbon bath, substan tia'lly as herein set forth.

21. A 'method for producing Mg casing for meat products which is translucent and nonputrescible, comprising forming a sheet of fibrous material prepared from mitzumata, kodzu, gampi or other similar plants into a tubular structure, applying identifying marks upon said tube, impregnating the mass with cellulose acetate in solution, substantially de-esterifying thecellulose acetate to form an insoluble deposit as herein set forth. v

22. The method of treating a sheet of matted. absorbent, vegetable fibres which comprises impregnating the sheet with a soluble cellulose derivative, a solution of which is prepared by dissolving in suitable solvents, allowing the .volatile solvents to evaporate, and then substantially completely regenerating the cellulose as an insoluble deposition upon the fibrous base.

rial which comprises impregnating a sheet of vegetable fibrous material with a solution of cellulose acetate and a suitable plasticizer to form a flexible transparent material unarifected by water. i

24. The method-of producing a container for edible products, which comprises impregnating a sheet of vegetable fibrous material with a soluble cellulose derivative, forming the material into a tube, making a closure at one end of the tube andthen regenerating the cellulose as an insoluble deposition upon the fibrous base. 25. The method of producing a container fo edible products, which comprises i'o'rminga sheet of vegetable fibrous material into a tube, impregnating said tube with a soluble-cellulose derivative, .drying the tube, and then regenerating the cellulose-as an insoluble deposition upon the fibrous base.

28. The method of producing a container for edible products, which comprises impregnating a sheet or vegetable fibrous material with a soluble cellulose derivative, forming the sheet'into a tube, and regenerating the cellulose derivative to form an insoluble deposition in'and upon the fibrous structure.

27. The method ..of producing asynthetlc gut havingthe properties of expanding when moistened and contracting when dried, which comprises impregnating a sheet of vegetable fibrous material with a solution oi! a cellulose derivatlveyand then substantially completely regencrating the cellulose to form an insoluble impregnation structure. N g 28. The methodof producing a'synthetic gut having the properties-of expanding when moistened and contracting when dried, which comprises treating a sheet of vegetable fibrous material with a solution of a cellulose derivative, and

substantially completely regenerating the celluof regenerated cellulou in the fibrous I 19, to form a homogeneous iabric coniprising an insoluble deposition of regenerated cellulose upon the fibrous sheet.

29. A- method of producing a material having the properties of a synthetic gut which comprises mixing vegetable fibres as such with a cellulose derivative, forming the mixture into a time, then substantially completely regenerating the cellugenerating the cellulose derivative to form a homogeneous fabric of regenerated cellulose united with the fibres.

- erated cellulose.

31. A method of producing a material having an ineradicable imprintation suitable for use as a covering for edible products which comprises impregnating a sheet of vegetable fibrous material with a cellulose derivative, applying identifying marks upon the dry impregnated material,

and then regenerating the cellulose to form a fibre and regen homogeneous combination of see 5 32. A container for food products comprising a base of matted vegetable fibres impregnated with an insoluble regenerated cellulose.

33. A casing material for meat products comprising a base of matted cellulosic fibres impregnated and coated with an insoluble regenerated cellulose. u

34. A casing material for meat products pomprising a base of vegetable fibrous material impregnated with a regenerated'cellulose, said material having the properties of expanding when moistened and contracting when dried.

35. A sausage casing comprising a tube of matted cellulosic'fibres impregnated with a regenerated cellulose, said casing' having the properties of expanding when moistened and con-- tracting when dried.

36. A casing for food products comprising a base. of vegetable fibrous material impregnated thereon an ineradicable imprintation.

37. An article of manufacture, a material having properties simulating those of a natural gut, comprising a vegetable fibrous base impregnated with regenerated cellulose. I

LEO A. GOODMAN.

with regenerated cellulose having therein or v 

